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WO2015095594A2 - Hydrocyanation hétérogène - Google Patents

Hydrocyanation hétérogène Download PDF

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Publication number
WO2015095594A2
WO2015095594A2 PCT/US2014/071274 US2014071274W WO2015095594A2 WO 2015095594 A2 WO2015095594 A2 WO 2015095594A2 US 2014071274 W US2014071274 W US 2014071274W WO 2015095594 A2 WO2015095594 A2 WO 2015095594A2
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Prior art keywords
alkaline earth
earth metal
alkali metal
reaction conditions
aluminum oxide
Prior art date
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Ceased
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PCT/US2014/071274
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WO2015095594A8 (fr
WO2015095594A3 (fr
Inventor
William J. Tenn Iii
Sudhir N. V. K. Aki
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Invista Technologies SARL Switzerland
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Invista Technologies SARL Switzerland
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Priority to EP14853170.0A priority Critical patent/EP3063126B1/fr
Priority to CN201480068171.6A priority patent/CN106170475B/zh
Priority to US15/102,792 priority patent/US9834506B2/en
Publication of WO2015095594A2 publication Critical patent/WO2015095594A2/fr
Publication of WO2015095594A3 publication Critical patent/WO2015095594A3/fr
Anticipated expiration legal-status Critical
Publication of WO2015095594A8 publication Critical patent/WO2015095594A8/fr
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/19—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and carboxyl groups, other than cyano groups, bound to the same saturated acyclic carbon skeleton
    • C07C255/22—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and carboxyl groups, other than cyano groups, bound to the same saturated acyclic carbon skeleton containing cyano groups and at least two carboxyl groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/08—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds
    • C07C253/10—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds to compounds containing carbon-to-carbon double bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B01J23/04—Alkali metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/232—Carbonates
    • B01J27/236—Hydroxy carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B01J27/26—Cyanides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers

Definitions

  • the present invention re!ates to an improved process for addition of hydrogen cyanide (HCN) across olefins and, in particular, to the use of a specific aluminum oxide to catalyze the reaction.
  • HCN hydrogen cyanide
  • adiponitrile an important intermediate in the manufacture of nylon-6,6 and related products, typically include a stage in which 3-pentenenitriie (3PN) or 4-pentenenitrile (4PN) is hydrocyanated in the presence of nickel (0) catalyst to form adiponitrile. It is known that c/s-2-pentenenitrile (c2PN) is formed as a byproduct during such a hydrocyanation. The formation of c2PN represents an adiponitrile yield loss in the process.
  • c2PN the accumulation of c2PN during the hydrocyanation reaction is undesirable because it behaves as a cata!yst poison.
  • the removal of c2PN is not straightforward. It can be separated from unreacted 3PN by distillation. Alternatively, it can be removed by reaction with an alkali metal sulfite and bisulfite solution but this can complicate the procedure.
  • c2PN rather than physically removing the c2PN, efforts have focused on converting it to a useful product. In this regard, it may be isomerized to 3PN, which can then be recycled back into the
  • Catalysts known for the Markovnikov addition of HCN to activated olefins tend to polymerize the activated olefin and the HCN as well.
  • Other catalysts capable of the Markovnikov addition of HCN to oiefins are not effective for non-activated olefins such as 3PN and 2-methyl-3- butenenitrile (2M3BN), which do not have an activating group in the alpha-position.
  • U.S. Patent No. 2,904,581 discloses that addition of HCN across activated oiefins can be accomplished using tetracyanonickelate (II) saits as catalyst.
  • U.S. Patent No. 7,371 ,884 discloses that certain amines are useful as homogeneous catalysts for the Markovnikov addition of HCN to acrylonitrile to produce succinonitri!e.
  • a separation process for separating the catalyst from the reaction product is required after the reaction.
  • U.S. Patent No. 8,394,981 discloses that certain homogenous biphosphite nickel complexes are useful as catalysts for the conversion of c2PN to greater than 90% adiponitrile, with minor formation of ethylsuccinonitrile (ESN).
  • ESN ethylsuccinonitrile
  • the present invention provides an improved process for addition of HCN across olefins, activated or not, at reaction conditions, in the presence of a specific aluminum oxide catalyst, more particularly describe hereinafter.
  • An embodiment of the present invention therefore, provides an improved process for addition of HCN across olefins which comprises contacting an olefin with hydrogen cyanide at reaction conditions in the presence of an aluminum oxide catalyst, wherein the aluminum oxide catalyst has total alkali metal and/or alkaline earth metal content, measured in the form of alkali metal oxide and/or alkaline earth metal oxide, of less than 3,000 ppm by weight total.
  • Another embodiment of the present invention provides an improved process for addition of HCN across olefins which comprises contacting an olefin with hydrogen cyanide at reaction conditions in the presence of an aluminum oxide catalyst, wherein the aluminum oxide catalyst has total alkali metal and/or alkaline earth metal content, measured in the form of alkali metal oxide and/or alkaline earth metal oxide, for example, sodium, potassium, and/or calcium, measured in the form of metal oxide, of less than 1000 ppm by weight.
  • Another embodiment of the present invention provides an improved process for addition of HCN across olefins which comprises contacting an olefin with hydrogen cyanide at reaction conditions in the presence of an aluminum oxide catalyst, wherein the aluminum oxide catalyst has total alkali metal and/or alkaline earth metal content, measured in the form of alkali metal oxide and/or alkaline earth metal oxide, for example, sodium, potassium, and/or calcium, measured in the form of metal oxide, of from 0 to 100 ppm, for example, from less than 25 to 100 ppm by weight.
  • Another embodiment of the present invention provides an improved process for addition of HCN across olefins which comprises contacting an olefin with hydrogen cyanide at reaction conditions including a temperature of from 50 to 450 °C and pressure from 760 to 5,000 mmHg in the presence of an aluminum oxide catalyst, wherein the aluminum oxide catalyst has total alkali metal and/or alkaline earth metal content, measured in the form of alkali metal oxide and/or alkaline earth metal oxide, for example, sodium, potassium, and/or calcium, measured in the form of metal oxide, of less than 3,000 ppm by weight total.
  • Another embodiment of the present invention provides an improved process for manufacturing ESN which comprises contacting c2PN, 3PN or a combination thereof with hydrogen cyanide at reaction conditions including a temperature of from 50 to 450 °C and pressure from 760 to 5,000 mmHg in the presence of an aluminum oxide catalyst, wherein the aluminum oxide catalyst has total alkali metal and/or alkaline earth metal content, measured in the form of alkali metal oxide and/or alkaline earth metal oxide, of less than 3,000 ppm by weight.
  • Another embodiment of the present invention provides an improved process for manufacturing DMSN which comprises contacting 2M2BN, 2M3BN or a combination thereof with hydrogen cyanide at reaction conditions including a temperature of from 50 to 450 °C and pressure from 760 to 5,000 mmHg in the presence of an aluminum oxide catalyst, wherein the aluminum oxide catalyst has total alkali metal and/or alkaline earth metal content, measured in the form of alkali metal oxide and/or alkaline earth metal oxide, of less than 3,000 ppm by weight.
  • the substantially pure aluminum oxide e.g. total alkali metal and/or alkaline earth metal content, measured in the form of alkali metal oxide and/or alkaline earth meta! oxide, of less than 3000 ppm, such as less than 1000 ppm, for example from 0 to 100 ppm by weight
  • used as catalyst is found to be an effective heterogeneous catalyst for the Markovnikov addition of HCN across olefins, activated or not, in this process.
  • the catalyst can be readily separated from the reaction product. Additionally, the catalyst is capable of converting both 2M3BN and 2- methyl-2-butenenitri!e (2M2BN) to dimethylsuccinonitriie (DMSN), and both 3PN and 2- pentenenitrile to 2-ethyIsuccinonitrile (ESN). Other traditional basic catalyst systems would not be effective for hydrocyanation of 3PN, or 2M3BN, which do not have an activating group alpha to the olefin. However, the catalyst for use herein is capable of isomerizing the unreactive 3PN or 2M3BN to the active 2-pentenenitriie or 2M2BN, respectively, in the present process.
  • the improved process of the invention comprises contacting an olefin with hydrogen cyanide at reaction conditions including a temperature of from 50 to 450 °C and pressure from 760 to 5,000 mmHg in the presence of an aluminum oxide catalyst, wherein the aluminum oxide catalyst has total alkali metal and/or alkaline earth metal content, measured in the form of alkali metal oxide and/or alkaline earth metal oxide, of less than 3,000 ppm by weight total.
  • activated olefin means an olefin that has an electron-withdrawing group in the alpha position.
  • Activated olefins for use as reactant in the present process include 2-pentenenitrile, and 2-methyl-2-butenenitriie.
  • Non-limiting examples of activated olefins for use herein are selected from the group consisting of c/s-2- pentenenitrile, 2-methyl-2-pentenenitrile, and combinations thereof.
  • ESN ethylsuccinonitrie
  • ESN is a product of the present process when the olefin is c2PN or 3PN.
  • DMSN means dimethylsuccinonitriie, e.g. 2,3- dimethy!succinonitrile.
  • DMSN is a product of the present process when the olefin is 2M2BN, e.g. c/s-2-methyl-2-butenenitrile or frans-2-methyl-2-butenenitri!e, or 2M3BN.
  • HCN hydrogen cyanide
  • hydrocyanic acid also known as hydrocyanic acid, prussic acid or formonitrile
  • used as a reactant in the process of this invention can be any of those commercially available.
  • HCN can be manufactured by cataiytically reacting ammonia and air with methane or natural gas.
  • the catalyst for use in the present invention is substantially pure aluminum oxide with total alkali metal and/or alkaiine earth metal content, measured in the form of alkali meta! oxide and/or alkaiine earth metal oxide, of less than 3,000 ppm by weight, such as less than 1000 ppm by weight, such as from 0 to 100 ppm, for example from less than 25 ppm to 100 ppm by weight.
  • the catalyst is capable of converting both 3PN and 2M3BN (which are not activated olefins) to 2- pentenenitri!e and 2M2BN, respectively, via isomerization. This enables hydrocyanation.
  • Catalysts for use in the present invention are commercially available.
  • suitable aluminum oxide catalysts for use in the process include AL-3995, AL-3996 and AL-4126, which are commercially available from Engelhard; and Cataiox SCFa-140 and Cataiox SBa-200, which are commercially available from Saso!.
  • Suitable aluminum oxide catalysts may be prepared using the techniques described in the "Puralox/Catalox ® High Purity activated aluminas" Sasol product brochure (http://www.sasoltechdata.com/tds/PURALOX_CATALOX.pdf), wherein aluminum alkoxide is used to produce synthetic boehmite of high purity.
  • Standard analytical techniques for determining metal content typically measure the content of alkali metal and/or alkaline earth metal impurities as the corresponding alkali metal and/or alkaline earth metal oxide.
  • the alkali metal and/or alkaline earth metal contents of the aluminum oxide catalyst used in the present process are as measured in the form of the corresponding alkali metal oxide and/or alkaline earth metal oxide.
  • the alkali metal is sodium
  • the sodium content is measured as Na 2 0.
  • Examples of techniques which may be used to determine the alkali metal and/or alkaline earth metal contents of the catalyst used in the present process include atomic absorption and flame photometry methods, such as described in Industrial Alumina Chemicals, ACS Monograph 184, Chanakaya Misra, American Chemical Society, 1986.
  • the catalyst is present in the process in a catalytical!y effective amount, which in the usual case means a concentration of from 5 % to 50 % by weight of the reaction mixture of HCN and olefin, preferably from 10 % to 40 %, even more preferably from 20 % to 30 %.
  • the catalyst for use in the present process can be in the form of powders or as shaped bodies, for example in the form of beads, cylindrical extrudates, spheres, rings, spirals, chopped film or granules.
  • the present invention process may be conducted in the liquid or vapor phase at reaction conditions including a temperature of from 50 to 450 °C and pressure from 760 to 5,000 mmHg.
  • reaction conditions include a temperature from 50 to 150 °C, such as from 55 to 125 °C, for example from 65 to 100 °C.
  • the process is run in the liquid phase at pressure from 760 to 5,000 mmHg, such as from 760 to 2,500 mmHg, for example from 1 ,500 to 2,500 mmHg.
  • reaction conditions include a temperature from >150 to 450 °C, such as from 160 to 225 °C, for example from 170 to 200 °C.
  • the process is run in the vapor phase at pressure from 760 to 5,000 mmHg, for example from 760 to 3,500 mmHg.
  • the process of the invention may be carried out in any reactor which is capable of containing a liquid or vapor medium and may be batch mode or continuous. When run
  • the process is preferably conducted in a continuously stirred tank reactor, with continuous stirring and with continuous addition of reactants and continuous removal of product.
  • the process can be run in a fixed-bed reactor, or bubble column.
  • the process may be carried out in a reactor capable of containing a liquid or vapor feed with the catalyst in a packed bed.
  • any suitable reactor it is preferable to adjust the temperature in the reaction zone, the concentration of reactants in the reaction zone, and the flow rate of the reactants into and products out of the reaction zone so that from 25 to 100 % by weight, preferably from 75 to 100 % by weight, of the HCN is converted on each pass through the reactor.
  • the residence time of the reactants in a continuous reactor can be, for example, from 5 minutes to 24 hours, such as from 30 minutes to 16 hours, for example from 1 to 4 hours.
  • Residence time (e.g. in minutes) is determined by measuring the volume (e.g. in milliliters) of the reaction zone and then dividing this figure by the flow rate (e.g. in milliliters per minute) of the reactants through the reactor.
  • the time required for the present improved process to provide a given conversion of HCN depends upon the conditions under which it is run. Time will therefore vary with temperature, pressure, concentrations of reactants and catalyst; and like factors.
  • the process is run to give a residence time from 5 minutes to 24 hours, such as from 30 minutes to 16 hours, for example from 0.5 to 8 hours, in the batch mode, the residence time is ordinarily from 1 to 4 hours.
  • the catalyst can be separated from the reaction mixture/product by filtration, decantation or centrifugation, and reused. If the process is run in a continuous fashion, the catalyst can simply be allowed to remain in the reactor while fresh reactants are fed in and product is removed.
  • Example 1 was repeated, except that 3PN was the olefin evaluated.
  • Example 3
  • Example 1 was repeated, except that magnesium oxide was used as the catalyst.
  • Example 4 is the same, except that magnesium oxide was used as the catalyst.
  • Example 3 was repeated, except that 3PN was the olefin evaluated.
  • Example 5
  • Example 1 was repeated, except that 2M3BN was the olefin evaluated.
  • Example 6
  • Example 1 was repeated, except that the temperature was maintained at 65 °C during the reaction.
  • Example 6 was repeated, except that aluminum oxide (F-200, product of BASF) having a Na 2 0 content of 3,000 ppm was used as the catalyst.
  • Example 8 aluminum oxide (F-200, product of BASF) having a Na 2 0 content of 3,000 ppm was used as the catalyst.
  • Example 3 was repeated, except that the temperature was maintained at 65 °C during the reaction.
  • Example 6 was repeated, except that zinc oxide was used as the catalyst.
  • Example 10 is zinc oxide
  • Example 6 was repeated, except that Amberlyst A-26 (product of Dow) was used as the catalyst.
  • Example 6 was repeated, except that nickel (II) cyanide tetrahydrate was used as the cataiyst.
  • Example 6 was repeated, except that nickel (II) cyanide was used as the catalyst.
  • Example 13
  • Example 6 was repeated, except that monoclinic zirconium oxide was used as the cataiyst.
  • the zirconium oxide was subjected to thermal treatment at 200 °C for 16 hours prior to use.
  • Example 13 was repeated, except that the monoclinic zirconium oxide was used directly as the catalyst without any thermal treatment prior to use.
  • Example 6 was repeated, except that tetragonal zirconium oxide was used as the catalyst.
  • the zirconium oxide was subjected to thermal treatment at 200 °C for 16 hours prior to use.
  • Example 15 was repeated, except that the tetragonal zirconium oxide was used directly as the cataiyst without any thermal treatment prior to use.
  • Example 17
  • Example 6 was repeated, except that hydrota!cite (product of SigmaAIdrich) was used as the catalyst.
  • Example 18 was repeated, except that the hydrotalcite used as the catalyst was calcined at 600 °C for 4 hours prior to use.
  • Example 6 was repeated, except that 1 ,3-cyclohexadiene was the olefin evaluated.
  • Example 21
  • c2PN c/s-2-pentenenitriie
  • 3PN cis- and trans-3-pentenenitrile, mixture of isomers 2M3BN - 2-methyl-3-butenenitrile
  • Example 22 The experimental conditions and results of Example 22 are shown in Table 2 below.
  • A is run time in hours;
  • B is reaction temperature in °C;
  • C is reaction pressure in mmHg;
  • D is HCN flow rate in mL/hour;
  • E is 2PN + 3PN conversion %;
  • F is 3PN conversion %;
  • G is ESN yield;
  • H is c2PN conversion based on ESN produced; and ⁇ ” is HCN conversion based on ESN produced.
  • 3PN conversion (3PN in feed - 3PN in product)/3PN in feed
  • 2PN + 3PN conversion ((2PN in feed + 3PN in feed)-(2PN in product + 3PN in product))/(2PN in feed + 3PN in feed)
  • HCN conversion based on ESN produced (moiar flow of ESN in product - moiar flow ESN in feed)/molar flow of HCN in feed
  • ESN yield (moiar flow of ESN in product - moiar flow ESN in feed)/(mo!ar flow of 3PN in feed + moiar flow of 2PN in feed)
  • c2PN conversion based on ESN (molar flow of ESN in product - molar flow ESN in feed)/moiar flow of 2PN in feed.
  • Example 22 the continuous fixed be reactor described in Example 22 was used for the vapor phase hydrocyanation of 2M2BN.
  • 55 grams of SCFa-140 alumina was used as the catalyst.
  • HCN flow rate was fixed at 0.75 mL/hour and the 2M2BN flow rate was maintained at 0.2 mL/minute.
  • the reaction temperature was maintained at 170 °C and the reactor pressure at 1285 mmHg.
  • Overall conversion of HCN under these conditions was found to be 70 % with the corresponding conversion of 2M2BN at 5 %, providing a yield of DMSN of 5 %.

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  • Organic Chemistry (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

La présente invention concerne un procédé amélioré d'addition de cyanure d'hydrogène sur des oléfines et, en particulier, l'utilisation d'un oxyde d'aluminium spécifique pour catalyser la réaction. Le catalyseur à base d'oxyde d'aluminium doit présenter une teneur totale en métaux alcalins et/ou alcalino-terreux, comme mesuré sous la forme d'oxydes de métaux alcalins et/ou alcalino-terreux, inférieure à 3 000 ppm en poids.
PCT/US2014/071274 2013-12-19 2014-12-18 Hydrocyanation hétérogène Ceased WO2015095594A2 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP14853170.0A EP3063126B1 (fr) 2013-12-19 2014-12-18 Hydrocyanation hétérogène
CN201480068171.6A CN106170475B (zh) 2013-12-19 2014-12-18 非均相氢氰化
US15/102,792 US9834506B2 (en) 2013-12-19 2014-12-18 Heterogeneous hydrocyanation

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US201361918152P 2013-12-19 2013-12-19
US61/918,152 2013-12-19

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WO2015095594A3 WO2015095594A3 (fr) 2015-08-13
WO2015095594A8 WO2015095594A8 (fr) 2016-10-06

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9834506B2 (en) 2013-12-19 2017-12-05 Invista North America S.A.R.L. Heterogeneous hydrocyanation

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2904581A (en) 1957-07-19 1959-09-15 Du Pont Process for the addition of hnc across the carbon to carbon double bond of an activated olefin
US3526654A (en) 1968-05-17 1970-09-01 Du Pont Isomerization of 2-pentenenitrile to 3-pentenenitrile
US4367179A (en) 1979-09-21 1983-01-04 The Standard Oil Company Hydrocyanation of olefinic alkyl esters
US20060194979A1 (en) 2003-04-22 2006-08-31 Basf Aktiengesellschaft Method for the isomerization of cis-2-pentenenitrile to form trans-3-pentenenitrile
US7371884B2 (en) 2001-12-11 2008-05-13 Dsm Ip Assets B.V. Process for preparing succinonitrile and use of succinonitrile
US8394981B2 (en) 2006-07-14 2013-03-12 Invista North America S.A R.L. Hydrocyanation of 2-pentenenitrile

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3063126B1 (fr) 2013-12-19 2018-08-01 INVISTA Textiles (U.K.) Limited Hydrocyanation hétérogène

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2904581A (en) 1957-07-19 1959-09-15 Du Pont Process for the addition of hnc across the carbon to carbon double bond of an activated olefin
US3526654A (en) 1968-05-17 1970-09-01 Du Pont Isomerization of 2-pentenenitrile to 3-pentenenitrile
US4367179A (en) 1979-09-21 1983-01-04 The Standard Oil Company Hydrocyanation of olefinic alkyl esters
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EP3063126B1 (fr) 2018-08-01
US9834506B2 (en) 2017-12-05
CN106170475B (zh) 2018-05-04
US20160311763A1 (en) 2016-10-27
CN106170475A (zh) 2016-11-30
WO2015095594A3 (fr) 2015-08-13

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